EP0539995B1 - Druckempfindlichen Klebstoff mit ausgezeichneter Wärmebeständigkeit, Klebeband welches diesen Klebstoff verwendet, und Methoden für ihre Herstellung - Google Patents

Druckempfindlichen Klebstoff mit ausgezeichneter Wärmebeständigkeit, Klebeband welches diesen Klebstoff verwendet, und Methoden für ihre Herstellung Download PDF

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Publication number
EP0539995B1
EP0539995B1 EP92118525A EP92118525A EP0539995B1 EP 0539995 B1 EP0539995 B1 EP 0539995B1 EP 92118525 A EP92118525 A EP 92118525A EP 92118525 A EP92118525 A EP 92118525A EP 0539995 B1 EP0539995 B1 EP 0539995B1
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Prior art keywords
meth
weight
acrylate
pressure
sensitive adhesive
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English (en)
French (fr)
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EP0539995A1 (de
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Takao C/O Nitto Denko Corporation Yoshikawa
Takaaki C/O Nitto Denko Corporation Moriyama
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Nitto Denko Corp
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Nitto Denko Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1809—C9-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2809—Web or sheet containing structurally defined element or component and having an adhesive outermost layer including irradiated or wave energy treated component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof

Definitions

  • the present invention relates to an acrylic pressure-sensitive adhesive having excellent heat resistance, which can endure the use at a high temperature of 100°C or higher and the use in a soldering step, an adhesive sheet formed by applying the adhesive on one surface or both surfaces of a sheet-form or tape-form backing, and also methods for producing the pressure-sensitive adhesive and the adhesive sheet.
  • An acrylic pressure-sensitive adhesive has excellent tackiness, cohesive force, aging resistance, etc., and has been wisely used.
  • the demand for a pressure-sensitive adhesive having a high heat resistance as a fixing tape for adhering parts or a masking tape in a soldering step in the case of assembling electronic parts, etc. has recently been increased.
  • An acrylic pressure-sensitive adhesive is generally prepared by copolymerizing an acrylic acid alkyl ester having from 2 to 14 carbon atoms in the alkyl moiety as the main component and if necessary, a small amount of a polar monomer such as acrylic acid, etc., together with monomer component(s) giving a high glass transition temperature, such as styrene, vinyl acetate, etc., for well-balancing the releasing characteristics, tack, etc. Also, for improving the heat resistance and the cohesive force, crosslinking is applied.
  • acrylic pressure-sensitive adhesive usually, after solution polymerizing a monomer in an organic solvent, the polymer formed is compounded with a tackifying resin, a crosslinking agent, etc., to provide an adhesive composition, and after coating the composition on a backing, a large amount of the organic solvent is removed by heating to provide a sheet-form or tape-form adhesive sheet.
  • the average molecular weight of the polymer formed is at most about 1,000,000. If the polymer is not crosslinked, the adhesive obtained is lacking in a holding property and even if the polymer is crosslinked, the cohesive force is lowered and holding property is greatly lowered, at a high temperature of higher than 100°C. Accordingly, when the adhesive is used for a fixing tape or a masking tape in a soldering step, there is a problem that slipping and oozing of adhesive occur during using such an adhesive sheet.
  • the low boiling organic solvent used in the production of the adhesive remains and the remaining solvent is vaporized and expanded at a high temperature to cause the problems of the occurrences of foaming, swelling, slipping, etc., at the adhered surface and also corrosion of electronic parts with the vaporized gas.
  • U.S. Patent 4,181,752 discloses a method of obtaining a pressure-sensitive adhesive without using an organic solvent by photo-polymerizing an acrylic acid alkyl ester and a monoethylenically unsaturated monomer on a backing. Also, a transfer type pressure-sensitive adhesive which is the same type of the adhesive as described above is first formed on a release liner and then transferred onto a backing is known.
  • the polymerization rate does not become 100% by no means and few percent by weight of the unreacted monomers remain.
  • the unreacted monomers thus remained not only cause a bad smell but also act as a plasticizer of the adhesive to greatly lower the cohesive force at a high temperature, cause swelling of the adhered surface by the volatilization of the monomers at a high temperature, and cause stains by the gas, which inhibit the use of the adhesive for heat resistance uses.
  • the polymerization rate For reducing the amount of the unreacted monomers, it may be considered to improve the polymerization rate by using a large amount of a photopolymerization initiator, but in such a case, the molecular weight of the polymer formed is lowered with the increase of the initiation radical concentration. As a result, the cohesive force of the adhesive at a high temperature is lowered and a high heat resistance which is desired in a soldering step, etc., has not yet been attained.
  • JP-A-2-60981 proposes that in a method of producing a pressure-sensitive adhesive tape by a photopolymerization, the photopolymerization is carried out in two separate stages for reducing the amount of the residual monomers by the improvement of the photopolymerization rate and for improving the productivity.
  • the object of the present invention is to provide a photopolymerization type acrylic pressure-sensitive adhesive capable of avoiding the occurrence of the problems caused by the remaining unreacted monomers or the formation of the low molecular weight materials and having a high heat resistance during the use at a temperature of higher than 100°C, and in particular, an excellent heat resistance under a very high temperature of up to 260°C as in the case of soldering step.
  • the inventors have found that in a photopolymerization type acrylic pressure-sensitive adhesive without need of using a low boiling organic solvent, by employing a method of removing remaining monomers after the photopolymerization by heat-drying in place of reducing the unreacted monomers by improving the photopolymerization rate as the above-described conventional manner, a pressure-sensitive adhesive having a large cohesive force at a high temperature and an excellent heat resistance is obtained with a restrained formation of low molecular weight materials at the photopolymerization and have succeeded to achieve the present invention based on this finding.
  • a pressure-sensitive adhesive having excellent heat resistance comprising a photopolymerized product of a composition comprising;
  • an adhesive sheet comprising a sheet-form or tape-form backing having formed one or both surfaces thereof a layer of the adhesive.
  • a method for producing a pressure-sensitive adhesive having excellent heat resistance which comprises irradiating a composition comprising;
  • a method for producing an adhesive sheet which comprises forming the layer of the pressure-sensitive adhesive produced by the above method on one or both surfaces of a sheet-form or tape-form backing.
  • the (meth)acrylic acid alkyl ester used in the composition of the present invention is the main component of the monomer mixture as component a).
  • a monofunctional unsaturated (meth)acrylate of a non-tertiary alkyl alcohol is preferably used as the (meth)acrylic acid alkyl ester, and the alkyl moiety thereof has from 2 to 14 carbon atoms.
  • Examples of such a monomer are ethyl (meth)acrylate, butyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate, and these monomers can be used alone or as a mixture thereof.
  • the monoethylenically unsaturated monomer copolymerizable with the (meth)acrylic acid alkyl ester is used to improve the adhesive property of the adhesive formed by the introduction of a functional group or a polar group or to control the glass transition temperature of the copolymer formed to thereby improve and modify the cohesive force and the heat resistance, by copolymerizing the same with the (meth)acrylic acid alkyl ester.
  • Examples of the monomer include acrylic acid, itaconic acid, sulfopropyl acrylate, a hydroxyalkyl acrylate, a cyanoalkyl acrylate, acrylamide, a substituted acrylamide, N-vinylcaprolactam, acrylonitrile, 2-methoxyethyl acrylate, glycidyl acrylate, vinyl acetate, and the like. These monomers are used alone or as a mixture thereof according to the purpose.
  • the content of the (meth)acrylic acid alkyl ester as the main component is from 70 to 100% by weight, and preferably from 85 to 95% by weight, and the content of the monoethylenically unsaturated monomer copolymerizable with the main component monomer is from 30 to 0% by weight, and preferably from 15 to 5% by weight.
  • composition of the present invention contains a small amount of a polyfunctional (meth)acrylate which is a crosslinking agent, as component b).
  • a polyfunctional (meth)acrylate which is a crosslinking agent
  • examples of the polyfunctional (meth)acrylate are trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,2-ethyleneglycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and the like.
  • the polyfunctional (meth)acrylate is used in an amount of from 0.02 to 5 parts by weight, and preferably from 0.1 to 3 parts by weight, per 100 parts by weight of the monomer mixture as component a).
  • the amount thereof may be large within the above-described range, and in the case of a trifunctional or higher functional (meth)acrylate, the amount thereof may be small within the above-described case.
  • the amount of the polyfunctional (meth)acrylate is less than 0.02 part by weight, the degree of crosslinking after the photopolymerization cannot be sufficiently increased, while if the amount of the polyfunctional (meth)acrylate is more than 5 parts by weight, there is a possibility of lowering the adhesive power of the adhesive obtained. Thus, the amount outside the above-described range is undesirable in this invention.
  • photopolymerization initiator used in the composition of this invention as component c) are benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, etc.; substituted benzoin ethers such as anisoin methyl ether, etc.; substituted acetophenones such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenonacetophenone, etc., substituted ⁇ -ketols such as 2-methyl-2-hydroxypropiophenone, etc.; aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride, etc.; and photoactive oximes such as 1-phenone-1,1-propanedione-1-(o-ethoxycarbonyl)oxime, etc.; and the like.
  • the photopolymerization initiator is used in an amount of from 0.01 to 4 parts by weight, and preferably from 0.05 to 1 part by weight, per 100 parts by weight of the monomer mixture as component a). If the amount of the photopolymerization initiator is less than 0.01 part by weight, a large amount of monomers is liable to remain, while the amount thereof is more than 4 parts by weight, the molecular weight of the polymer is lowered and thus the cohesive force of the adhesive is liable to lower.
  • the monomer mixture of component a) is first mixed with the photopolymerization initiator as component c) and the pre-mixture formed is partially polymerized to form a syrup-form product having a coatable viscosity range of from 500 to 5,000 centipoises.
  • the pre-mixture of the monomer mixture and the photopolymerization initiator is mixed with a thixotropic agent such as fumed silica to form a coatable syrup-form product.
  • the composition for photopolymerization is prepared.
  • various conventional additives such as a filler, a pigment, an aging inhibitor, a tackifying resin, etc., in the ranges of not hindering the photopolymerization by the irradiation of ultraviolet rays.
  • the composition thus prepared is irradiated with ultraviolet rays to form a photopolymerized product.
  • the irradiation of ultraviolet rays is carried out in an oxygen-free atmosphere displaced with an inert gas such as a nitrogen gas or in a state of shielding air by coating the composition with an ultraviolet ray-permeable film.
  • Ultraviolet rays used for the photopolymerization are electromagnetic radiations having a wavelength range of from 180 to 460 nm, but electromagnetic radiations of wavelengths of longer than or shorter than the above-described wavelength range may be used.
  • an irradiation means such as a mercury arc lamp, a carbon arc lamp, a low-pressure, intermediate-pressure or high-pressure mercury lamp, a metal halide arc, or the like is generally used.
  • the intensity of the ultraviolet rays can be suitably selected by controlling the distance between the light source and an article to be irradiated or by controlling the voltage of the light source, but taking the irradiation time (productivity) into consideration, it is usually desirable to use weak light of from 0.1 to 7 mW/cm2.
  • the photopolymerization product thus obtained by the irradiation with ultraviolet rays has a sufficiently high molecular weight and also has a high degree of crosslinking such that the content of solvent-insoluble components becomes at least 60% by weight, and preferably from 70 to 95% by weight, by being internal-crosslinked with the crosslinking agent as component b).
  • the photopolymerization product usually remain from 1 to 5% by weight of unreacted monomers.
  • the present invention it is an important feature to remove the remaining unreacted monomers by heat-drying to the extent that the content of the remaining monomers becomes less than 5,000 ppm, and preferably less than 3,000 ppm.
  • Drying by heating in the present invention is usually carried out using a drying furnace but it is particularly preferred to use a hot air circulating drying furnace having a far infrared heater. This is because the photopolymerized product can be dried with a good efficiency in a short period of time by heating from the inside with the far infrared heater and diffusion of the circulating hot air from the surface.
  • the drying condition depends upon the faculty of the drying furnace but the drying temperature and the drying time are usually from 100 to 150°C and from several tens seconds to several minutes, respectively.
  • the photopolymerization product having the solvent-insoluble components of at least 60% by weight and the remaining amount of the unreacted monomers of less than 5,000 ppm thus obtained has good tackiness, adhesive strength, and cohesive force, in particular large cohesive force at a high temperature, and can be widely used as an acrylic pressure-sensitive adhesive having an excellent heat resistance for a heat-resistance use of at least 100°C as a fixing tape for adhering electronic parts and a masking tape in a soldering step.
  • the adhesive sheet of the present invention is prepared by forming the acrylic heat-resistant adhesive having excellent heat resistance obtained by the above-described method on one or both surfaces of a sheet-form or tape-form backing according to the above-described uses.
  • a sheet-form or tape-form backing As the backing, porous materials such as nonwoven fabrics, papers, etc., or plastic films such as polyester films, polyimide films, etc., are used and for heat-resistance uses, heat-resistant backings such as polyimide films, etc., are particularly preferably used.
  • the thickness of the backing is usually from 25 to 125 »m and also the thickness of the layer of the acrylic pressure-sensitive adhesive is usually from 25 to 100 »m.
  • the production of the adhesive sheet of the present invention can be carried out by forming the layer of the acrylic pressure-sensitive adhesive having a desired thickness on a release liner by the method described above and transferring the adhesive layer onto one or both surfaces of a backing.
  • the adhesive sheet of the present invention may be produced by a method of directly impregnating or coating the backing with the composition for photopolymerization without using a release liner, irradiating the composition with ultraviolet rays to form the photopolymerized product having solvent-insoluble components of at least 60% by weight, and drying the photopolymerized product by heating to reduce the content of the remaining unreacted monomers to less than 5,000 ppm.
  • the above-described method can be properly employed according to the kind of the backing, etc.
  • a photopolymerized product having a high molecular weight and being highly crosslinked can be obtained and also by reducing from 1 to several percents by weight of unreacted monomers remaining in the photopolymerized product to a slight content of less than 5,000 ppm by heat-drying the photopolymerized product, an acrylic pressure-sensitive adhesive highly satisfying high tackiness, adhesive strength, and cohesive force, in particular, having excellent cohesive force at high temperature, and capable of sufficiently enduring the use in a heat-resistant field can be provided since the adhesive contains less low molecular weight materials and unreacted monomers, which lower the cohesive force, and also contains less unreacted monomers which vaporize in the case of heating at a high temperature, and also an adhesive sheet having formed thereon the above-de
  • a pre-mixture was prepared using 60 parts of isononyl acrylate, 28 parts of butyl acrylate, 12 parts of acrylic acid, and 0.05 part of 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651, trade name, made by Ciba-Geigy Corporation) as a photopolymerization initiator.
  • Irgacure 651 trade name, made by Ciba-Geigy Corporation
  • composition was coated on a polyimide film of 25 »m in thickness, and photopolymerized by irradiating the coated composition with ultraviolet rays of 400 mj/cm2 by a high-pressure mercury lamp having an intensity of 5 mW/cm2 under a nitrogen gas atmosphere to form a layer of the photopolymerized product having a thickness of 50 »m.
  • the content of the remaining monomers in the photopolymerized product was 30,000 ppm. Further, the content of the solvent-insoluble components was 71% by weight.
  • the polyimide film having formed thereon the layer of the photopolymerized product was placed in a hot air circulating dryer and heat-treated at 130°C for 5 minutes to remove the remaining monomers in the photopolymerized product to provide a pressure-sensitive adhesive sheet having the layer of the adhesive wherein the content of the remaining monomers was 2,600 ppm.
  • a pre-mixture was prepared using 90 parts of 2-ethylhexyl acrylate, 10 parts by weight of acrylic acid, and 0.05 part of Irgacure 651 (the photopolymerization initiator described above). By exposing the pre-mixture to ultraviolet rays in an nitrogen gas atmosphere, the premixture was partially polymerized to provide a coatable syrup having a viscosity of about 5,000 centipoises.
  • the partially polymerized syrup was added 1.0 part of 1,6-hexanediol diacrylate as a crosslinking agent and 0.05 part of the additional Irgacure 651 (the above-described photopolymerization initiator), followed by mixing to provide a composition.
  • the composition was coated on a polyimide film of 25 »m in thickness and the coated composition was photopolymerized by irradiating the coated layer with ultraviolet rays of 700 mj/cm2 by a high-pressure mercury lamp having an intensity of 5 mW/cm2 under a nitrogen gas atmosphere to form a layer of the photopolymerized product having a thickness of 50 »m.
  • the content of the remaining monomers in the photopolymerized product was 17,000 ppm. Further, the content of solvent-insoluble components of the photopolymerized product was 84% by weight.
  • Example 2 By treating the polyimide film having formed thereon the layer of the photopolymerized product in a hot air circulating dryer as in Example 1, the remaining monomers in the photopolymerized product was removed to provide an adhesive sheet having formed thereon the layer of the adhesive containing the remaining monomer components of 1,400 ppm.
  • the solvent-insoluble components in the photopolymerized product were 35% by weight and the content of the remaining monomers after the heat treatment was 2,000 ppm.
  • the mixture was coated on a polyimide film of 25 »m in thickness and dried in a hot air dryer at 130°C for 5 minutes to provide an adhesive sheet having formed thereon the adhesive layer of 50 »m in thickness.
  • the solvent-insoluble components in the adhesive layer were 68% by weight, the content of remaining toluene was 800 ppm, and the content of the remaining monomer components was 110 ppm.
  • the composition was coated on a polyimide film of 25 »m in thickness and irradiated with ultraviolet ray (wavelength of 360 nm) having an intensity of 5 mW/cm2 for 1 minute in a nitrogen gas atmosphere (1st irradiation stage).
  • ultraviolet ray wavelength of 360 nm
  • the content of the remaining monomers was 2.8% by weight.
  • the coated composition was further irradiated with ultraviolet rays using a super-high-pressure mercury lamp of an intensity of 15 mW/cm2 (2nd irradiation stage), and the remaining monomers were polymerized to provide an adhesive sheet.
  • the amount of the remaining monomers was 1,100 ppm, and the solvent-insoluble components were 74% by weight.
  • the adhesive strength was measured according to the method of JIS Z-1522 using a stainless steel plate as a material being adhered. The adhesive strength was shown by g/20 mm width.
  • Each adhesive sheet (10 mm in width) was bonded to one end in lengthwise of a stainless steel plate (30 mm ⁇ 120 mm ⁇ 3.0 mm) having a mirror-plane surface such that the adhered area became 20 mm ⁇ 10 mm, after allowing to stand the assembly for 30 minutes, a load of 500 g was applied at 100°C, and the time required for falling the adhesive sheet by slipping was measured.
  • the mark (*) in Table 2 shows that the sample fell by cohesive failure and the mark ( ⁇ ) shows that the adhesive sheet fell with prints leaving on the surface of the stainless steel plate.
  • a cut sample of 10 mm ⁇ 10 mm of each of the adhesive sheets prepared in the above examples and comparison examples was adhered on a stainless steel plate (50 mm ⁇ 50 mm ⁇ 0.4 mm) having a mirror-plane surface by means of a hand roller with a great care such that air bubbles did not enter the adhered surface, and after allowing to stand the assembly for 30 minutes at room temperature, the stainless steel plate was treated by floating the adhered sheet above on a molten soft solder bath at 260°C for 10 seconds (molten soft solder floating test).
  • the adhesive sheets obtained in Examples 1 and 2 wherein the contents of the solvent-insoluble components and the remaining monomers are in the specific ranges defined by the present invention have a good adhesive strength as well as are excellent in heat-resisting holding property at a high temperature and have an excellent heat resistance capable of enduring a molten soft solder bath floating test.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Claims (15)

  1. Druckempfindlicher Klebstoff bzw. Haftklebstoff mit ausgezeichneter Wärmebeständigkeit, umfassend ein Photopolymerisationsprodukt einer Zusammensetzung umfassend:
    a) 100 Gewichtsteile eines Monomergemisches, umfassend 70 bis 100 Gew.-% eines (Meth)acrylsäurealkylesters mit im Durchschnitt 2 bis 14 Kohlenstoffatomen in dem Alkylbestandteil und 30 bis 0 Gew.-% eines monoethylenisch ungesättigten Monomers, das mit dem (Meth)acrylsäurealkylester copolymerisiert werden kann,
    b) 0,02 bis 5 Gewichtsteile eines polyfunktionellen (Meth)acrylats als Vernetzungsmittel, und
    c) 0,01 bis 4 Gewichtsteile eines Photopolymerisationsinitiators,
    worin der Gehalt an in Lösungsmittel unlöslichen Komponenten mindestens 60 Gew.-% beträgt und die verbleibende Menge an nicht umgesetzten Monomeren weniger als 5000 ppm beträgt,
    welcher durch Bestrahlen der Zusammensetzung und Trocknen des daraus hervorgehenden Photopolymerisationsprodukts bei 100-150°C während mehreren zehn Sekunden bis mehreren Minuten erhalten werden kann.
  2. Druckempfindlicher Klebstoff nach Anspruch 1, worin der (Meth)acrylsäurealkylester ein monofunktionelles ungesättigtes (Meth)acrylat eines nicht-tertiären Alkylalkohols ist.
  3. Druckempfindlicher Klebstoff nach Anspruch 1, worin der (Meth)acrylsäurealkylester mindestens ein Bestandteil, ausgewählt aus der Gruppe bestehend aus Ethyl(meth)acrylat, Butyl(meth)acrylat, Isoamyl(meth)acrylat, n-Hexyl(meth)acrylat, 2-Ethylhexyl(meth)acrylat, Isooctyl(meth)acrylat, Isononyl(meth)acrylat, Decyl(meth)acrylat und Dodecyl(meth)acrylat ist.
  4. Druckempfindlicher Klebstoff nach Anspruch 1, worin das monoethylenisch ungesättigte Monomer mindestens ein Bestandteil, ausgewählt aus der Gruppe bestehend aus Acrylsäure, Itaconsäure, Sulfopropylacrylat, Hydroxyalkylacrylat, Cyanoalkylacrylat, Acrylamid, substituiertem Acrylamid, N-Vinylcaprolactam, Acrylnitril, 2-Methoxyethylacrylat, Glycidylacrylat und Vinylacetat, ist.
  5. Druckempfindlicher Klebstoff nach Anspruch 1, worin die Menge des (Meth)acrylsäurealkylesters 85 bis 95 Gew.-% beträgt und die Menge des monoethylenisch ungesättigten Monomers 15 bis 5 Gew.-% beträgt.
  6. Druckempfindlicher Klebstoff nach Anspruch 1, worin das polyfunktionelle (Meth)acrylat ausgewählt ist aus der Gruppe bestehend aus Trimethylolpropan-tri(meth)acrylat, Pentaerythrit-tetra(meth)acrylat, 1,2-Ethylenglycol-di(meth)acrylat und 1,6-Hexandiol-di(meth)acrylat.
  7. Druckempfindlicher Klebstoff nach Anspruch 1, worin die Menge des polyfunktionellen (Meth)acrylats 0,1 bis 3 Gewichtsteile beträgt.
  8. Druckempfindlicher Klebstoff nach Anspruch 1, worin der Photopolymerisationsinitiator gewählt wird aus der Gruppe bestehend aus Benzoinethern, substituierten Benzoinethern, substituierten Acetophenonen, substituierten α-Ketolen, aromatischen Sulfonylchloriden und lichtempfindlichen Oximen.
  9. Druckempfindlicher Klebstoff nach Anspruch 1, worin die Menge des Photopolymerisationsinitiators 0,05 bis 1 Gewichtsteile beträgt.
  10. Druckempfindlicher Klebstoff nach Anspruch 1, worin der Gehalt an in Lösungsmittel unlöslichen Komponenten 70 bis 95 Gew.-% beträgt.
  11. Druckempfindlicher Klebstoff nach Anspruch 1, worin die verbleibende Menge der nicht umgesetzten Monomere weniger als 3000 ppm beträgt.
  12. Klebefolie, umfassend einen Träger mit einer Schicht aus einem druckempfindlichen Klebstoff nach einem der Ansprüche 1 bis 11 auf einer oder beiden Oberflächen davon.
  13. Verfahren zum Herstellen eines druckempfindlichen Klebstoffs nach einem der Ansprüche 1 bis 11, welches das Bestrahlen einer Zusammensetzung, umfassend:
    a) 100 Gewichtsteile eines Monomergemisches, umfassend 70 bis 100 Gew.-% eines (Meth)acrylsäurealkylesters mit im Durchschnitt 2 bis 14 Kohlenstoffatomen in dem Alkylbestandteil und 30 bis 0 Gew.-% eines monoethylenisch ungesättigten Monomers, das mit dem (Meth)acrylsäurealkylester copolymerisiert werden kann,
    b) 0,02 bis 5 Gewichtsteile eines polyfunktionellen (Meth)acrylats als Vernetzungsmittel, und
    c) 0,01 bis 4 Gewichtsteile eines Photopolymerisationsinitiators,
    mit Ultraviolettstrahlen zum Bilden eines Photopolymerisationsprodukts mit einem Gehalt an in Lösungsmittel unlöslichen Komponenten von mindestens 60 Gew.-%, und das Trocknen des Photopolymerisationsprodukts durch Erwärmen, um den Gehalt an nicht umgesetzten Monomeren auf weniger als 5000 ppm zu verringern, umfaßt.
  14. Verfahren zum Herstellen einer Klebefolie nach Anspruch 12, welches das Beschichten oder Imprägnieren von einer oder beiden Oberflächen eines Trägers in Folienform oder Bandform mit einer Zusammensetzung umfassend:
    a) 100 Gewichtsteile eines Monomergemisches, umfassend 70 bis 100 Gewichtsteile eines (Meth)acrylsäureesters mit im Durchschnitt 2 bis 14 Kohlenstoffatomen im Alkylbestandteil und 30 bis 0 Gew.-% eines monoethylenisch ungesättigten Monomers, das mit dem (Meth)acrylsäurealkylester copolymerisiert werden kann,
    b) 0,02 bis 5 Gewichtsteile eines polyfunktionellen (Meth)acrylats als Vernetzungsmittel, und
    c) 0,01 bis 4 Gewichtsteile eines Photopolymerisationsinitiators,
    das Bestrahlen der aufgetragenen oder imprägnierten Zusammensetzung mit Ultraviolettstrahlen zum Bilden eines Photopolymerisationsprodukts der Zusammensetzung mit einem Gehalt an in Lösungsmittel unlöslichen Komponenten von mindestens 60 Gew.-%, und das Trocknen des photopolymerisierten Produkts durch Erwärmen, um die verbleibende Menge an nicht umgesetzten Monomeren auf weniger als 5000 ppm zu verringern, umfaßt.
  15. Verfahren zum Herstellen einer Klebefolie nach Anspruch 12, welches das Bilden einer Schicht aus einem druckempfindlichen Klebstoff mit einem Gehalt an in Lösungsmittel unlöslichen Komponenten von mindestens 60 Gew.-% und einem Gehalt an nicht umgesetzten Monomeren von weniger als 5000 ppm auf einer Abziehschicht durch Beschichten der Abziehschicht mit einer Zusammensetzung umfassend:
    a) 100 Gewichtsteile eines Monomergemisches, umfassend 70 bis 100 Gew.-% eines (Meth)acrylsäurealkylesters mit im Durchschnitt 2 bis 14 Kohlenstoffatomen in dem Alkylbestandteil und 30 bis 0 Gew.-% eines monoethylenisch ungesättigten Monomers, das mit dem (Meth)acrylsäurealkylester copolymerisiert werden kann,
    b) 0,02 bis 5 Gewichtsteile eines polyfunktionellen (Meth)acrylats als Vernetzungsmittel, und
    c) 0,01 bis 4 Gewichtsteile eines Photopolymerisationsinitiators,
    das Bestrahlen der Schicht mit Ultraviolettstrahlen, das Trocknen der Schicht durch Erwärmen, und das Übertragen der so gebildeten druckempfindlichen Klebstoffschicht auf einen Träger in Folienform oder Bandform umfaßt.
EP92118525A 1991-10-31 1992-10-29 Druckempfindlichen Klebstoff mit ausgezeichneter Wärmebeständigkeit, Klebeband welches diesen Klebstoff verwendet, und Methoden für ihre Herstellung Expired - Lifetime EP0539995B1 (de)

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JP313235/91 1991-10-31
JP3313235A JP2922036B2 (ja) 1991-10-31 1991-10-31 耐熱性にすぐれた感圧性接着剤およびその接着シート類の製造方法

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US5462977A (en) 1995-10-31
US5623000A (en) 1997-04-22
JPH05117593A (ja) 1993-05-14
JP2922036B2 (ja) 1999-07-19
DE69202852T2 (de) 1995-10-26
DE69202852D1 (de) 1995-07-13
EP0539995A1 (de) 1993-05-05

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